JPH02200654A - Method of hydroformylation - Google Patents

Abstract

PURPOSE: To efficiently hydroformylate an olefinic unsaturated org. reactant by bringing a liquid phase olfinic unsaturated org. reactant into contact with a mixture of carbon monoxide and hydrogen in the presence of a heterogenous catalyst composed of a specific rhodium complex.

CONSTITUTION: A liquid phase olefinic unsaturated org. reactant is brought into contact with a mixture of carbon monoxide and hydrogen in a polar solvent characterized by the substantial incompatibility with the org. reactant phase in the presence of an effective amt. of a heterogenous catalyst wherein a soln. of at least one rhodium complex is fixed on the surface of a solid to be subjected to hydroformulation reaction to obtain the objective compd. The above mentioned catalyst is prepared, for example, by impregnating the surface of a solid such as silica with the rhodium complex in a volatile solvent and, after the solvent is evaporated, steam is condensed on the surface of the solid to form the aq. soln. film of the above complex thereon.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a catalytic reaction method for the hydroformylation of olefinically unsaturated organic compounds, in particular comprising a solution of a rhodium complex in a polar solvent supported on a solid surface. 3, the invention also relates to the catalyst system used in the process and the method for preparing the catalyst system.

Hydroformylation is a well-known commercially practiced method for converting olefinically unsaturated organic compounds into the corresponding aldehydes or alcohols by contacting and reacting with a mixture of carbon monoxide and hydrogen. . - In boat fishing, hydroformylation is expressed by the following ten reaction equations.

Since and/or hydroformylation involves some degree of generalization at the carbon-carbon double bond position, several other aldehyde and alcohol structures are often formed in addition to those mentioned above. In the above reaction formula, R, R, R and R4 independently represent an organic group or other substituent, such as a hydrogen or halogen atom, a hydroxyl group, a carbonyl group or a carboxyl group, which are present at the double bond site. It does not interfere with the desired reaction.

Currently, rhodium-catalyzed hydroformylation reactions are most commonly used for the conversion of low carbon number (e.g. C3-C5) olefins to aldehydes, but are also used for the conversion of a wide range of other olefinically unsaturated reactants. It is known that it can also be applied.

In conventional methods, hydroformylation reactions exclusively use homogeneous rather than heterogeneous catalysts. Although the use of homogeneous catalysts in hydroformylation provides relatively high reactivity and selectivity under mild reaction conditions, it is associated with inherent difficulties in recovering the homogeneous catalyst from the reaction products. When dealing with homogeneous catalysts containing rhodium compounds and/or complexes, it is essential to recover the catalyst very efficiently, considering the value of the metal. Furthermore, the purity of the product is also important, as it determines whether the catalyst can be efficiently removed from a particular chemical by rhodium-catalyzed hydroformylation. It has been found that currently available methods for removing homogeneous catalysts are often difficult and/or expensive. In many cases,
The need for catalyst recovery has limited opportunities for commercial use of rhodium catalysts.

Although the development of heterogeneous catalysts has been desired for many years due to inherent problems in the use of homogeneous hydroformylation catalysts, attempts to use heterogeneous rhodium catalysts have been limited to the removal of rhodium from the solid support during the process. So far there has been little success due to insufficient leaching or catalytic activity.

In another aspect, the invention relates to a hydroformylation process carried out in the presence of a catalyst, such as a rhodium complex, in solution in a polar solvent (eg water). The solution is
Substantially immiscible with the olefinically unsaturated organic reactant phase. U.S. Pat. No. 4,248,802 describes a hydroformylation catalyst system containing a rhodium-containing aqueous solution of certain sulfonated phosphine compounds. Rhodium is present either in the form of metallic rhodium deposited on a support or in the form of water-soluble compounds or complexes. This patent does not suggest a catalyst in which the rhodium complex solution is supported on a solid. Also, this patent does not specify an aqueous rhodium complex solution that is substantially immiscible with the organic reactant phase. However, U.S. Pat. This can be said to be an advantage.

Borowski et al., Nouveau, J., Chemi.
e 2.145 (1978) also describes a method for the preparation of rhodium complexes dissolved in water and their use as hydroformylation catalysts. During hydroformylation, an aqueous complex solution is incorporated and dispersed into an immiscible organic reactant phase. This document does not contemplate the immobilization of such complexes on the surface of a solid support.

Here we have discovered that a heterogeneous catalyst containing a rhodium complex in solution in a polar liquid phase immobilized on a solid surface effectively catalyzes the hydroformylation of olefinically unsaturated organic reactants.

According to the invention, therefore, there is provided a process for the hydroformylation of liquid phase olefinically unsaturated organic reactants, comprising the steps of: a) being substantially immiscible with said organic reactant phase; The above organic reactants are combined with a mixture of carbon monoxide and hydrogen under hydroformylation conditions in the presence of an effective amount of a heterogeneous catalyst having a solid surface on which a solution of one or more rhodium complexes in a polar solvent is immobilized. A method is provided comprising: contacting and reacting; and b) removing the catalyst from the resulting mixture of reaction products.

The present invention's use of rhodium complexes immobilized on the surface of a specified solid support has a number of differences and advantages compared to hydroformylation catalysts in conventional methods. For example, a method for supporting a rhodium complex on a solid surface involves forming an interfacial region between an immobilized polar liquid phase containing the rhodium complex and a liquid organic reactant phase, and this region is
This is significantly larger than the interfacial area obtained by simple stirring of two free (unsupported) immiscible liquid phases.

Furthermore, the separation of the active rhodium complex from the organic reactants by the interface between the polar phase and the organic phase changes the catalyst activity and selectivity. Furthermore, it is of particular importance that the effective immobilization of the catalytically active rhodium complex on the solid support facilitates the practical use of rhodium in the hydroformylation reaction and the separation of the products. be.

The invention is preferably practiced with a catalyst in which the polar solvent contains at least as much water as the water of hydration of the rhodium complex present, and more preferably with a solvent consisting essentially of water.

The present invention is based on discoveries involving the use of specific types of catalysts in hydroformylation processes. Apart from the use of such catalysts, the process of the invention generally involves the use of reactants, reaction mixtures, etc., as is known in the art of hydroformylation, particularly hydroformylation promoted with rhodium n complex catalysts. and reaction conditions as appropriate. However, the reactants, reaction steps and reaction conditions can be specified as preferred embodiments.

That is, for example, the present invention can be applied to the hydroformylation of organic reactant compounds having a small number (or one) of olefinic unsaturation, i.e., having at least one carbon-carbon double bond in the molecule. The olefin must be non-reactive with water and/or other polar solvents contained in the immobilized catalyst solution.

In certain preferred practical IM embodiments, the invention is preferably applied to the hydroformylation of olefinic unsaturation in aliphatic (cyclic or acyclic) hydrocarbons. Monoolefins such as propylene, butylene, pentene and hexene are some examples of suitable lower alkene reactants. The invention is equally applicable to the hydroformylation of a wide range of alkenes, for example those having 3 to 30 carbon atoms, more preferably 3 to 25 carbon atoms. In fact, olefin reactants of any carbon number, including those with carbon numbers greater than 30, may be used as olefin reactants for this purpose, as long as they are liquid under the reaction conditions. Can be done. Solvents for the olefinic reactants may also be used. Olefins with higher carbon numbers,
For example, application of the present invention to 06 and higher olefins provides substantial advantages not available with conventional homogeneous catalysts, whose use is generally limited to lower olefins due to the operations required for catalyst recovery. . The feed hydrocarbons can include both branched and straight chain compounds having one or more olefinic moieties.

As with conventional rhodium complex-catalyzed hydroformylation, the method of the present invention is equally applicable to the hydroformylation of non-hydrocarbon olefinic linkages, although again the reactants must be liquid under the reaction conditions. and preferably has 3 to 30 carbon atoms, particularly 3 to 25 carbon atoms. Thus, for example, the present invention provides hydroformylation of olefinically unsaturated alcohols, aldehydes, acids, ketones, esters, and other olefinic compounds having substituents whose position and nature do not interfere with the desired hydroformylation. used appropriately.

In the case of reactant molecules with multiple double bonds, it is necessary to specify that they are non-conjugated.

Thus, for example, 1,5-hexadiene is suitable for hydroformylation according to the invention, while 1,3-butadiene is not.

The unsaturated carbon-carbon bonds of the reactants may be located at the terminal portion of the molecule, such as in 1-octene, or in 4-octene.
- May be internally located, such as decene or cyclohexene.

Polymeric materials are also included within the range of suitable olefinically unsaturated reactants for purposes of this invention.

Mixtures of various olefinically unsaturated compounds can be present in the organic liquid reactant phase of the process and hydroformylated in the process of the invention. Depending on the relative reactivity of the individual olefinic compounds, some or all of them may be converted to aldehydes and/or alcohols in the reaction step. Again depending on their relative reactivities, one or more of the olefinic moieties (non-military) of the polyolefin can be hydroformylated in the practice of this invention.

In the practice of this invention, the olefinically unsaturated reactant (
and the hydroformylation products formed, and optionally other compatible additives, solvents, etc.) must be substantially immiscible with the polar phase of the supported catalyst. Solvents and/or ligands are intentionally incorporated into the reactant phase to counteract this tendency to the extent that the reactant phase has some tendency to dissolve and remove the polar solvent and/or ligand from the aqueous phase of the catalyst. can do.

As a condition regarding the immiscibility of the organic reactant phase, additives, solvents or other such that the reaction system has properties that result in a non-negligible degree of miscibility between the water v1 catalyst phase and the organic reactant phase. It is important to note that the ingredients must not be contained in amounts that would cause this to occur. This is in contrast to traditional hydroformylation methods, which use organic co-solvents, phase transfer agents, etc., e.g. lower alcohols, to increase the solubility between the polar catalyst phase and the organic reactants. .

As in conventional hydroformylation, the olefinically unsaturated reactants are contacted with a mixture of carbon monoxide and hydrogen. As is commonly known in such hydroformylation processes, water may be introduced as a source of hydrogen reactant.

Although not required, the H2/CO mixture is present in the hydroformylation reactor in stoichiometric excess (e.g., 1 to 10 times the amount required) relative to the olefinically unsaturated reactant (to convert). is desired (taking into account the number of double bonds in the reactants), and - a molar excess of hydrogen to carbon oxide is present (e.g. H2:CO molar ratio ranging from 1 to 10) - Boat fishing. However, the total amount of CO/H2 mixture relative to the amount of olefinic reactant compound, and the ratio of CO to H2 in this mixture, are both not critical in the practice of the mixture of the present invention, and both may be used as desired. Variations can be made (and according to principles well known in the art) to adjust the reaction rate and yield of the desired product. Of course, each conversion to alcohol requires 001 molecules and 822 molecules for each double bond converted.
molecules are required. When producing aldehydes, the reaction involves 001 molecules and 82 molecules for each double bond converted.
One molecule is consumed.

The olefinically unsaturated reactant is subjected to hydroformylation reaction conditions in the presence of a portion of the specified immobilized polar phase catalyst sufficient to effect the desired hydroformylation.
Contact with a mixture of carbon monoxide and hydrogen is necessary.

Suitable supported polar phase catalysts contain a solution of a rhodium complex in a polar solvent immobilized on a solid surface. As used herein, the term "complex J" means a metal atom, in particular a rhodium atom, in combination with molecules or atoms of one or more F electron-rich "ligands" which can exist independently. I want to be understood. In other words, a "ligand" has a pair of electrons that can bond with a metal atom to form a complex. As used herein, the term "immobilized" refers to the action of chemical or physical forces that prevent the rhodium complex in polar solution from migrating to the organic reactant phase.

To immobilize a solution of a rhodium complex in a polar solvent, the solid surface must be compatible with partial or complete coverage by the polar solution.

Many of the ligands suitable for the formation of water-soluble rhodium complexes have surface activity, promoting wetting of solid surfaces by solutions.

Furthermore, the solid must be such that it can maintain its structural integrity in the presence of the polar catalyst solution and the organic reactant phase. Suitable solid surfaces are, for example, silica, alumina, titania, aluminobosphate, carbon, polymers and compacted clays.

Although not essential in principle to the practice of the invention, porous solids are preferred in order to provide a larger surface area at the interface with the organic reactant phase. Furthermore, it has been observed that when using porous supports with a wide pore size distribution, the catalyzing polar solution is no longer homogeneously distributed over the surface, but is instead distributed over smaller pores. Consequently, a relatively thick coating of the aqueous phase can prevent organic reactants from accessing these smaller pores, while the surface of the larger pores is not covered by the aqueous phase; It is not fully covered. For these reasons, solid porous supports having pores of relatively uniform diameter are more preferred. Pore size range 10~3.000
Examples include commercially available silica-rich glasses of Angstrom. Preferably, the majority of the pores in the porous support have a pore size greater than 20 angstroms.

While not intending to limit the present invention to any one reaction theory or reaction mechanism, hydroformylation involves essentially two immiscible phases: (1) an organic reactant phase, and (2) a supported catalyst. It is thought that this occurs at the interface between the polar phase and the polar phase. The catalyst of the invention has an aqueous phase supported on a solid surface,
It provides an interfacial area between the organic reactant and the aqueous phase that is significantly F above the level expected theoretically from simple agitation of the two immiscible phases.

Examples of suitable polar solvents for rhodium complexes are water and other polar solvents such as (poly)alkylene glycols,
Includes aqueous solutions of one or more solvents selected from the group consisting of alcohols, diols and polyols. Generally, the solvent must be one in which the O-Dium complex is adequately soluble and substantially immiscible with the phase of the olefinically unsaturated reactant (and the hydroformylation product after formation). Must.

Preferably, the polar rhodium complex solution of the catalyst contains at least some water, in particular an amount of water corresponding at least to the water of hydration of the rhodium complex. Preferably, the polar solvent contains mostly water, in parts by weight, and more preferably the solvent is mostly water. Most preferred is the use of a solvent consisting of water.

Although a variety of rhodium complexes are known in the art to catalyze the hydroformylation of olefinically unsaturated organic reactants, conventional catalyst complexes generally do not allow the introduction of organic reactants and products into the phase. It is formed from a ligand that facilitates the solubilization of the rhodium complex. However, for purposes of the present invention it is necessary that the ligand be suitably soluble in the polar phase of the supported catalyst and preferably substantially insoluble in the organic reactant phase. It is.

Rhodium catalysts that are soluble in water and other polar solvents are known in the art. Typically, the complex is a ligand, such as a tertiary alkyl or arylphosphine ligand, provided that one or more of the alkyl or aryl groups is
one or more substituents (e.g. one or more carbonyl, carboxyl, nitro, amino, hydroxy, sulfonate,
1 by adding a bosphate, sulfate, ether, polyether or quaternary ammonium group)
It is formed from a Gantt that is "functionalized", thereby increasing its solubility in polar solvents.

Rhodium complexes are formed by contacting the ligand with a rhodium complex or salt, such as rhodium carbonyl, rhodium chloride, or rhodium diamine.

One particularly preferred class of water-soluble rhodium complexes are those derived from the sulfonated phosphine ligands described in the aforementioned US Pat. No. 4,248,802.

Such ligands are defined in the U.S. patent specification as having the following formula: and R2 are the same or different and are straight or branched alkyl groups having from 1 to 4 carbon atoms. M represents a group selected from the group consisting of alkali metals, alkaline earth metals, lead, a carbocyclic ring having from 6 to 10 carbon atoms, in which Ar1, Ar2 and Ar3 are the same or interdependent; (carbocyc I ic ) represents an aryl group, Yl, Y2 and Y3 are the same or different, and each represents a linear or branched alkyl group having 1 to 4 carbon atoms; Alkoxy group, halogen atom, -OH group, -CAN group, -N0
2 groups and the formula -NR1R2 (where R1 (where R1R4
, R5 and R6 are the same or different and each is a straight-chain or branched alkyl group having 1 to 4 carbon atoms). is a cationic group, ml, m2 and m3 are the same or different, 0 to 5
is an integer, and n , n and n3 are the same\
12 or different integers from O to 3, and at least one of nl, n and n3 is 1 or more].

Preferred boss fins of formula (2) are Ar1, Ar2 and Ar
3 is phenyl, ml, m2 and m are O,
n , n and n3 are O or 1, and n
This is a compound in which the sum of 2+n3 is 1 to 3, and the 503H group is in the meta position.

Particularly preferred are phosphines of formula (1) in which M is sodium.

Immobilization of Catalyst Although the concentration of rhodium complex in the polar solution is not critical to the present invention, solutions with relatively high concentrations of complex are desirable for higher catalytic activity. moreover,
The complex is believed to be less stable in less concentrated solutions. A catalyst containing an amount of immobilized rhodium complex greater than the solubility limit of the rhodium complex in the available polar solvent (i.e. containing the complex in a polar solvent solution and at the same time a separate undissolved component immobilized on the solid) Catalysts such as those containing In either case, however, the catalyst preferably contains an activating amount of water, ie an amount corresponding to or more than the water of hydration of the complex. The presence of at least an activating amount of a polar solvent (e.g. water)
A high catalytic activity is obtained compared to that of another catalyst without an aqueous solution immobilized on a solid. Typically, the catalyst is activated by the presence in the immobilized catalyst solution of a polar solvent (eg water) in an amount of 10% or more by weight relative to the amount of rhodium complex present. The optimum IIm of the rhodium complex in solution varies with the choice of the particular ligand.

The catalyst used in the method of the present invention is catalytically effective even in relatively small amounts. Thus, for example, batch reactions according to the present invention are generally suitably carried out with a catalyst containing as little as 0.00001 part of rhodium (calculated as metal) per 1 part of olefinically unsaturated reactant type. . Amounts of catalyst containing at least 0.0001 parts by weight of rhodium by this method of calculation are considered particularly preferred.

The heterogeneous catalysts used in the process of the invention are novel and constitute another aspect of the invention. Therefore, the present invention
A solution of one or more organometallic complexes of rhodium in a polar solvent provides a heterogeneous catalyst suitable for use in the process of the invention, where the solution has a fixed solid surface.

In one preferred method for preparing catalysts suitable for use in the present invention, a solid surface is first impregnated with a rhodium complex and then a sufficient amount of rhodium is added to dissolve all or a portion of the complex. A polar solvent is added, thereby forming a coating of the solution that covers all or a portion of the available solid surface area. In the initial impregnation, the complex can be introduced into the pores on the porous solid, for example, as a solution in any convenient solvent. This solvent is removed by evaporation under relatively mild conditions and preferably in vacuum F, depositing the complex on the exterior and pore surfaces. The polar solvent for the final complex solution can then be added in a controllable manner, for example in the form of a vapor that condenses on the surface and dissolves all or part of the rhodium complex. This two-step operation for immobilizing and coating a complex solution on a solid surface is advantageous over the ancient one-step process of coating the solid directly with a rhodium complex solution in a polar solvent. In one-step impregnation and immobilization, it is often difficult to control the uniform distribution of the solution on solid surfaces, especially porous solid surfaces. However, catalysts prepared by one-step direct immobilization operations are within the scope of the present invention, as are catalysts prepared by other immobilization methods apparent to those skilled in the art. Logi・
When an aqueous solution is used to impregnate a solid with a cum complex, the catalyst solution is characterized by relatively uniform dispersion by drying while adjusting the activation amount of water to remain in the solution. A catalyst is obtained.

When a polar solution is deposited on a solid surface, or alternatively when a solution is formed on a solid surface, the pores of the porous solid catalyst component are filled or blocked, thereby increasing the efficiency between the polar and organic phases. It is preferable to perform the loading operation carefully so as not to reduce the interface area. Preferably the loading of the solution comprises a coating of the polar solution on the solid and an organic phase.
This is done in such a way that the final catalyst maintains a wide interfacial area during the process. However, the invention also encompasses catalysts in which the immobilization solution fills the pore volume of the porous support.

A two-step process for the preparation of heterogeneous catalysts suitable for use in hydroformylation processes is yet another and preferred embodiment of the invention. The invention therefore further provides the step of impregnating the external and pore surfaces of the porous solid supermediate support with a solution of at least one water-soluble organometallic complex of rhodium in a volatile solvent, evaporating the solvent from the impregnated catalyst. A method for preparing an aqueous phase catalyst supported on a support, comprising the steps of: evaporating the solvent from the impregnated catalyst; and condensing water vapor on the solid surface to form an aqueous solution coating of a rhodium complex on the surface. I will provide a.

Hydroformylation conditions suitable for the purposes of the present invention are:
It corresponds to that used in conventional hydroformylation processes catalyzed by rhodium complexes, e.g. at temperatures of 50-250°C and pressures of 1-202 bar (1-202 bar).
This includes conditions such as 00atI11).

Preferably the process temperature is 50-150°C, but 70-150°C.
Temperatures in the range 140°C and 1 bar to 138.8
Pressures in the range of 4 to 2000 psio are considered more preferred. Care must be taken to operate at sufficiently low temperatures and high pressures to maintain the polar solvent of the rhodium complex solution in a liquid state, while at the same time operating at temperatures below the temperature at which the ligand complex begins to decompose. .

Because of their heterogeneous solid nature, the identified catalysts can be easily applied in stirred vessels or fixed or fluidized bed reactors, and can be applied in either batch processes or continuous single culm operations. The process of the present invention is suitably carried out using methods and equipment conventionally used in hydropormylation processes. After the hydroformylation reaction, the catalyst is easily separated from the product using gravity precipitation, centrifugation, filtration and/or one or more other solid-liquid separation methods. The organic product mixture is recovered and optionally processed for separation and purification of the products, separation and reuse of the reactants, and the like.

The invention will be further illustrated by the following examples.

Example 1 - Catalyst Preparation The solid support was porosity-set glass CP G-240.
(obtained from Electro-Nucleonics, Inc., 120/200 mesh size, average pore size 23
7 people ±4.3%, pore volume 0.95ae/g, surface area 77
．． 5f/9>, the supported aqueous phase catalyst of the present invention was prepared using hydride carbonyl tris(sodium triphenylphosphine trisulfonate) rhodium(1) as the organometallic complex.

Triphenyl small sphine trisulfonate was first synthesized by the following steps. Eight grams of triphenylphosphine were degassed in vacuo, blanketed with argon, and cooled to 10° C. in a water bath. Next, add sulfuric acid (95%) while stirring vigorously.
．． 7 m was added dropwise.

(Concentrations herein are not given in weight percent unless otherwise stated.) Stirring was continued until complete dissolution.

A mixture of 10.8 d of 30% sulfur trioxide and 16.67 d of 99% sulfur trioxide in sulfuric acid was added slowly dropwise with stirring. The temperature of the water bath was increased to 20.5°C over 7 hours. After 12 hours, the reaction was stopped by cooling to 6°C, and then 200 d of degassed cold water was added. The aqueous bone solution was extracted twice with 50 ml of tributyl phosphate. in a stirred water bath under an argon atmosphere.
The tributyl phosphate layer was neutralized by vigorous stirring with a 50% aqueous sodium hydroxide solution. The resulting sludge was rinsed with 100 Id of ethyl ether for each wash.
It was washed twice and then vacuum dried. Next, mix the sludge with distilled water
5tnR. By adding 75 d of anhydrous methanol, a brown precipitate was precipitated, which was filtered off. The mother liquor was evaporated under vacuum to obtain high purity sodium triphenylphosphine trimetasulfonate. Yield calculated for trinoenylbosphine starting material is 2
It was 9%.

Next, hydride carbonyl tris(sodium triphenylphosphine trisulfonate) (1) was prepared from triphenyl small sphine trisulfonate. For this purpose, 50 R g of dicarbonyl rhodium (1) acetylacetonate were added to 1 d of a degassed solution of 400 μl of sodium triphenylphosphine trisulfonate in vigorously stirred water. After completely dissolving, at room temperature and atmospheric pressure, hydrogen and carbon oxide (1'2C
Stirring was continued for 6 hours under an atmosphere with a molar ratio of J to O of 1:1). The resulting solution was filtered under nitrogen to remove the small amount of metallic rhodium present. 8 d of absolute ethanol saturated with (4)-1,,/CO mixture (1:1 molar ratio)
was added to precipitate the desired chain. The mixture was centrifuged and the precipitate was collected, which was then washed with absolute ethanol and dried under vacuum. Analysis revealed that it was a highly purified hydride carbonyl tris(sodium triphenylphosphine trisulfonate) rhodium(1) complex, and no phosphine oxide was detected.

This complex was then loaded onto a solid catalyst support. The solid complex was converted into trinoenylphosphine trisulfonate 410m
g in 25 d of degassed water and the resulting solution was poured into 8.8 g of CP G-240 solid that had been previously degassed and blanketed with argon. The resulting slurry was degassed under vacuum and blanketed with 1 atmosphere of argon. Finally, the slurry is dried under vacuum, approximately 2.9 g based on the weight of dry solids.
wt% (or about 2.8 wt% based on total catalyst weight)
The moisture content was adjusted to . The obtained substance is kept at normal pressure,
Stored at room temperature under an atmosphere of H2 and Co (1:1 mol).

Example 2 - Addition of Water Twenty milligrams of the solution prepared in Example 1 was placed in a microreactor submerged in a thermostatic bath at 30<0>C.

After drawing a vacuum, the catalyst was allowed to absorb moisture. a reactor;
A flask of degassed water, also immersed in a thermostatic bath at 30° C., was connected to the vapor space. After 90 minutes of exposure to water vapor, argon was introduced into the system and the reactor was closed.

The hydration catalyst of Example 2 had a water content of about 8.5%, calculated based on dry weight.
5% by weight (approximately 7.5% by weight calculated based on the total weight of the catalyst)
It contained.

Example 3 - Hydroformylation of Oleyl Alcohol Under an atmosphere of dry nitrogen, a microreactor was charged with 0.10 grams of the catalyst prepared in Example 1 and o.io grams of oleyl alcohol (25% by volume in cyclohexane). The reactor was then flushed with a H2/CO mixture (1:1 mol) and 57.9 bar (825 p
sig). The reactor was heated to 100° C. and maintained at that temperature with stirring for 5.5 hours. Analysis of the product revealed that 96.6% of oleyl alcohol
% conversion, confirming that the double bond of the alcohol was hydroformylated.

Example 4 - Evaluation of Rhodium Leaching At the end of the hydroformylation reaction of Example 3, the slurry of reactants, products and catalyst in the reactor was filtered to separate the supported catalyst particles. Enough additional stone oleic alcohol was added to the filtered liquid to bring the concentration from 3.4% to 46%. The formed solution was then subjected to the same temperature, H2/CO pressure, and stirring conditions as the hydroformylation reaction mixture of Example 3 at 9 pm. No increase in aldehyde concentration was observed.

To further investigate whether any rhodium was lost from the catalyst during the reaction of Example 3, the cyclohexane solvent was evaporated from the solution. 0.10 al. of 1-hexane to the oleyl alcohol reactant and its hydroformylation product remaining after cyclohexane evaporation. was added. The reactor was flushed with hydrogen and 5.1 bar (60 ps
io). The temperature was raised to 100° C. and the contents of the reactor were stirred for 2 hours during hydrogenation. No hydrogenation of 1-hexane was observed, indicating that there was no zerovalent metallic rhodium in the system.

These experiments demonstrate that the catalytically active rhodium complex remains effectively immobilized on the solid surface of the catalyst during the hydroformylation step of the present invention.

Examples 5-8 A series of other catalysts suitable for use in the present invention were prepared according to the methods of Examples 1 and 2.

However, they were prepared by varying the exposure time to water vapor during hydration of the impregnated support, thus varying the portion of water in the aqueous phase of the final catalyst. The set conditions for the hydration step in the preparation of each of the catalysts of Examples 1.2 and 5-8 are shown in the table below.

The water content of the final catalyst is the weight percent of water relative to the total catalyst weight.
It was expressed as

5 0.75 2 1.5 8 6.5 2.8 7.5 Examples 9 to 14 - Hydroformylation of 1-octene In Examples 9 to 14, in Examples 1.5.2 and 6 to 8, respectively Each of the supported aqueous phase catalysts prepared as described were evaluated as catalysts for the process of the invention, particularly for the hydroformylation of 1-octene.

For each hydroformylation reaction, 0.40 d of a solution of 1-octene (20% by volume in degassed cyclohexane) was introduced into the microreactor containing the prepared catalyst. The reactor was flushed with a H2/CO mixture (1:1 mole), pressurized to 52.7 bar (750 psig) with a 2/CO mixture, and stirred at 70 DEG C. in an oil bath. After 5 hours the reaction was stopped and the product mixture was analyzed for 1
The conversion of -octene to C9 aldehyde and the ratio of straight to branched carbon chains of C9 aldehyde were investigated. The results of the hydroformylation reaction are summarized in the table below.

Examples Examples of catalysts used Octene conversion Branched chain No. of linear aldehyde No.
(%) Ratio to aldehyde 1
0 2, 1 38.5 2.9 62.5 2.7 45 2.85 5, 9 2.5 4.1 2.5 Examples 15 to 18 By a method similar to that described in Example 9, Other olefinically unsaturated reactant compounds were hydroformylated in the presence of the catalyst described in Example 1. The olefinic reactant was introduced as a 20 volume % solution in Schiff [1 hexane] in Example 15 and as a 50 volume % solution in Examples 16, 17 and 18. Other reaction conditions and results for each of these examples are summarized in the table below.

1-octene C-jasmondicyclopentadiene dicyclopentadiene o,ooi O,0002 0,0002 0,0002 51,0 (725) 52,7 (750) 52.7 (750) 52.7 (750) 98.7 圀、5 14.4 Straight/branched ratio=1.8 Feather% dialdehyde 0.7% dialdehyde 9.2% dialdehyde Example 19 - Solubility of rhodium complexes in polar solvents For the preparation of a catalyst suitable for use in the process, it is necessary that the ligand used to form the rhodium complex be dissolved in the catalytic polar solvent. A series of experiments were conducted to determine the solubility of sodium triphenylphosphine direto sulfonate ligand prepared as described in Example 1 in several polar solvents. Ligand solubility was measured at 25°C and expressed as grams of ligand dissolved in 1 g of water, or ethylene glycol or glycerol. The results of these experiments are shown in the table below and show that the ligand is soluble in many different polar solvents.

ethylene glycol Grise 0-le Ligand solubility q ligand/g solvent 0.52-0.85 0.05-0.08 Approximately 0.13

Claims (10)

[Claims] (1) A process for the hydroformylation of liquid-phase olefinically unsaturated organic reactants, comprising the steps of: a) a hydroformylation process in a polar solvent, characterized in that it is substantially immiscible with the organic reactant phase; Contacting and reacting the organic reactant with a mixture of carbon monoxide and hydrogen under hydroformylation conditions in the presence of an effective amount of a heterogeneous catalyst having a solid surface on which a solution of one or more rhodium complexes is immobilized. and b) removing the catalyst from the reaction product mixture obtained. 2. The method of claim 1, wherein the polar solvent contains an amount of water at least equal to the amount of water of hydration of the one or more rhodium complexes. (3) The method according to claim 1 or 2, wherein most of the polar solvent is water. (4) The method according to any one of claims 1 to 3, wherein the solid surface has a porous solid. 5. The method of claim 4, wherein the porous solid has a relatively uniform pore size. (6) The method according to any one of claims 1 to 5, wherein the olefinically unsaturated reactant has a carbon number ranging from 3 to 30. (7) The method according to any one of claims 1 to 6, wherein the one or more rhodium complexes include one or more rhodium sulfonated phosphine complexes. (8) step a) at a temperature in the range of 50 to 250°C, and 1
8. Process according to any one of claims 1 to 7, carried out under pressure in the range -202 bar. (9) A heterogeneous catalyst suitable for use in the method of claim 1, having a solid surface on which a solution of one or more organometallic complexes of rhodium in a polar solvent is fixed. (10) impregnating the exterior and pore surfaces of the porous solid catalyst support with a solution of at least one water-soluble organometallic complex of rhodium in a volatile solvent; evaporating the solvent from the impregnated catalyst; A method of making a supported aqueous phase catalyst comprising the step of condensing water vapor onto a surface to form an aqueous coating of a rhodium complex on the surface.